Amino ethers



Patented Feb. 19, 1946 UNITED STAT AMINO ETHEBS Clinton W. MacMullen and Herman A. Bruson, Philadelphia, Pa., assignors to Riihm & Haas Company, Philadelphia, Pa... a corporation of Delaware No Drawing. Application June 2, 1942,

Serial No. 445,452

12 Claims.

This invention relates to aryl aliphatic ethers which contain an aromatic nucleu substituted by an aminomethyl group and to a process for preparing such ethers. More particularly this invention relates-to ethers of the formula (ZCHz) AIXAY wherein Z is a secondary amine group, a secondary amine group in its salt form, a tertiary amine group, a tertiary amine group in its salt form, or a quaternary ammonium group, n is an integer having a value of one or two, Ar is a carbocyclic aromatic nucleus, X isoxygen or sulfur, A is an alkylene group, the chain or which may be interrupted by oxygen or sulfur, andY is apolar group based upon the elements carbon, hydrogen, halogens, oxygen, and nitrogen, including such'groups as OH, --O-alkyl, --O- aryl, CO-alkyl, --C-aryl, -OCO-alkyl, OC0-aryl, -COOH, -COO-allcyl, -CONHR', -CONHR", halogen, NRR", or NR'R"R"' anion, R'--R"' representing hydrogen or aliphatic, cycloaliphatic, arylaliphatic, heterocyclic, or aryl groups.

The aminomethyl ethers of this invention may be prepared by reacting an amine with an aryl aliphatic ether having a nuclear halomethyl substituent in the presence of a strong base, such as "sodium hydroxide, potassium hydroxide, benzyl trimethylammonium hydroxide, barium hydroxide, calcium hydroxide, etc.

Asa halomethyl ether there may be used any of the ethers described in the applications having Serial Numbers 415,034, 415,035, and 415,036, all filed September 2, 1941, now issued as United States .Patents Nos. 2,291,526, 2,291,527, and 2,291,528, respectively, issued July 28, 1942, and in United States Patent No. 2,266,737, issued December 23,-1941.

the valkyl group contains from one to eighteen carbon atoms,

(ClCHz) nArOCH2CH2CO-a1kyl Typical halomethyl aryl aliphatic ethers which are suitable as starting materials include such compounds as the following:

(ClCI-Iz') nAiOCHzCHaOH where n has a value of one or two, BrCH2CaH4OCH2CH2OCHa BrCHzCsI-hOCHzCHzOCsHs BrCHaCeI-I4OCH2CH2OCsH4CH2Br where m is aninteger from oneto ten or more, and

arylaliphatic ethers there is used a primary,

CICI-Iz) nArOCH2CH2COO-a1kyl of a hydrogen halide and formaldehyde. This requirement excludes phenolic hydroxyl, amino, diazo, and aldehyde groups. The aromatic nucleus may be mononuclear or polynuclear, as in benzene, naphthalene, phenanthrene, anthracene,

. dipheny l, etc.-

As reactant withone of the above halomethyl secondary, or tertiary amine to yield second or tertiary amines, their salts, or a quaternary ammonium salt. Furthermore, a product in the form of a tertiary amine may be converted by reaction with an alkylating oraralkylating agent into a quaternary ammonium salt. The reacting amines may be members or the aliphatic, arylaliphatlc, cycloaliphatic, or aryl series or may contain substituents from two or more 01' these series. Typical amines include methylamine, ethylamine, isopropylamine, butylamine, amylamine, octylamine, isooctylamine, caprylamine, decylamine, dodecylamine, octadecenylamine, octadecylamine, allylamine, methallylamine, hydroxyethylamine, hydroxypropylamine, benzylamine, methylbenzylamine, aniline, chloroaniline, cyclohexylamine,

methylcyclohexylamine, dimethylamine, diethyl amine, dibutylamine, diethanolamine, dimethallylamine, diisoo'ctylamine, methyl benzylamine, dicyclohexylamine, methylaminobenzene, cyclic amines such as morpholine, piperidine, pyrrolidine, etc., trimethylamine, benzyld methylamine, dodecyldimethylamine, cyclohexyldimethylamine, dimethylaminobenzene, triamylamine, pyridine, etc. In fact, any mono-amine appears to be useiul in forming the aminomethyl aryl aliphatic ethers of this invention. It will be noted that, in the cases or such amines as morpholine and pyridine, the groups attached to the nitrogen are dior tri-valent groups which form heterocycles with the nitrogen.

The reaction between halomethyl arylaliphatic ether and amine is carried out by reacting said ether with an amine in the presence of a base at a temperature between about 20 C. and about 250 0. If desired, the reaction may be performed in the presence of a solvent. such as dioxane, toluene, water, or the like. when several types of labile halogens are present in the ether, the reaction may be so conducted as to replace one type or all of the halogens. Ii. the reaction is carried out above about 100 0., the various labile halogens are replaced by amine groups. Between 20' C. and about 100 0.. however, only the halogen or the halomethyl groups reacts In a similar way the reaction product may be varied in the case 01' the ethers having -COOH, or COOR, or -OCOR groups by variations in temperatures of reaction. Thus, in the lower range amines react only with the halogen 'oi' the halomethyl group, whereas in the upper temperature range there occurs not only the reaction with the halomethyl group but also reaction with the carboxyl group leading to monoor di-substituted carboxylic amides and to alcohols.

Because of the diilerence in reactivity of the diflerent ypes of labile halogens, they may be replaced with one type of amino nitrogen group or with diiierent such groups. Thus, the compound R'R"NCH:ArXC:H4Clmay be formed below 100 C. and this reacted above 100 R'R"NCH2A1XC2H4NR"'R"".

Tertiary amines prepared by reaction of halomethyl ether and secondary amine may be converted to the corresponding quaternar ammonium salt by reaction with such compounds as the dialkyl sulfates, as, for example, diethyl sul-' fate, alkyl halides as, for example, methyl iodide, bromide, or chloride, benzyl halides, esters, as, for example, methyl Iormate, ethyl chloroacetate, or methyl-p-toluene sulfonate, alkyl halomethyl ethers as, for example, bromomethoxybutane,- or a halomethyl aryl ether, such as chloromethyl phenoxyethyl chloride, etc.

When a salt of an amine is desired, it may be formed by the addition of an acid to an amine. Salts of both inorganic and organic acids may be prepared.

The amino ethers of this invention may be used as textile finishing agents, disinfectants, bacteri- C. to form cides. wetting agents, detergents, insecticidal preparations, drugs. fungicides, etc.

73 grams of diethylamine was added to a cold solution oi 40 grams of sodium hydroxide in 120 gram 01' water. To this cold mixture was added with stirring '70 grams of chloromethyl o-cresoxy ethoxy ethyl chloride at 6 to 11 C. The milky viscous mixture was. stirred 25 hours during which the'temperature rose to 27 C. The lower aqueous layer wa discarded, and the oil taken up in benzeneand washed twice with water. The crude amine was converted to its hydrochloride with hydrochloric acid, and the aqueous mixture steam-distilledto remove insoluble impurities. The residue stood a few days, and the slightly turbid aqueous solution was decanted from a few grams oi heavy insoluble oil, and clarified by agitation with an adsorbent clay. The clear amber filtrate was neutralized with sodium hydroxide solution, and the tree" amine liberated was taken up in benzene and ,washed. The solvent was distilled oil in vacuo, and the residual oil clarified by stirring with 2.5 grams of activated charcoal. The 42 grams of yellow oil obtained after filtration corresponded in composition to diethylaminomethyl o-cresoxy ethoxy ethyl chloride having the formula:

(Cal-Is) aNCHaCaHs (CH3) OC2H4OC2H4C1 A quaternary ammonium salt was prepared by refluxing 10 grams of the diethylaminomethyl ocresoxy ethoxy ethyl chloride with 11 grams of ethyl bromide for one hour'at 54 C. The excess ethyl bromide was then distilled out, leaving a viscous paste which did not crystallize when cooled. The (p chloroethoxy-ethoxy) methylbenzyl triethylammonium bromide hadthe following formula:

Another quaternary ammonium derivative was prepared by warming 10 grams oi the diethylaminomethyl o-cresoxy ethoxy ethyl chloride with 5 grams of benzyl chloride for eight hours at 70 C. The (p -chloroethoxy-ethoxy) -methyl-benzyl ,diethyl benzyl ammonium chloride was a viscous orange'oil having the formula:

A quaternary ammonium salt was prepared by heating; 6 grams of the diethylaminomethyl ocresoxy ethoxy ethyl chloride with 4 grams of decyl chloromethyl ether for four and a half hours at C. The viscous red paste obtained was soluble in water with suds. and the product had the formula:

ethoxy ethyl chloride, 30 grams of paraformalde-' hyde, and 200 grams of ethylene dichloride was stirred and saturated with gaseous hydrogen 7 chloride for seven hours'at 50-53 C. The reaction mixture was washed with ice water, dried with anhydrous sodium sulfate, filtered, and the solvent distilled off in vacuo leaving 140 grams of clear amber oil.

This was crude chloromethyl p-tert-octyl phenoxy ethoxy ethyl chloride which was added during 35 minutes to a mixture or 360 grams of 25% dimethylamine solution and 80 grams of sodium hydroxide'at 3-5 C., and the, mixture stirred nine hours at 548 C. Th oil layer. was converted to the soluble amine hydrochloride with hydrochloric acid, and the aqueous solution steam-distilled to remove non-soluble impurities. The residual viscous, amber, clear solution was neutralized with sodium hydroxide to liberate the amine which was taken up in benzene, washed twice with water, dried with anhydrous sodium sulfate, filtered, and the solvent distilled ofl in vacuo. The dimethylaminomethyl p-tert-octyl phenoxy ethoxy ethyl chloride was obtained as a clear amber, viscous oil, having the formula:

(cm) 2NCH2C6H3(CIH1'I) ocimocimci A quaternary ammonium salt was prepared by heating 7.5 grams of dimethylaminoniethyl ptert-octyl phenoxy ethoxy ethyl chloride with 3 grams of methallyl chloride at 90 C. for 5 hours. The (-p-chlcroethoxy-ethoxy) -p-tert-octyl-'benzyl dimethyl methallyl ammonium chloride was obtained as a clear yellow viscous oil, soluble in water with suds, having the formula:

Example 3 44 grams of morpholine was mixed with asolution of 20 grams of sodium hydroxide in 49 grams of water, and to this cold mixture was added with stirring 118 grams of chloromethyl p-tert-octyl phenoxy ethoxy ethyl chloride during 30 minutes at 55-70 C. The turbid brown mixture was stirred five and a half hours at 70-60" C. To the cooled reaction mixture was added 80 cc. of concentrated hydrochloric acid and 200 cc. of water, and the mixture steam distilled to remove insoluble impurities. The residue was diluted with water and clarified by stirring twice with and grams of activated charcoal, respectively. The aqueous solution was filtered, and neutralized to liberate the amine.

The amine was taken up in benzene and washed three times with water. The benzene was distilled of! in vacuo leaving 93 grams of viscous amber oil, consisting of morpholinomethyl p-tertoctyl phenoxy ethoxy ethyl chloride which had the formula:

CHQCH:

CHsCHa ncmclmwimnocimocmlci octyD-benzyl decy'l-oxy-mcthyl morphollnium chloride had the followina formula:

prepared by heating 8 grams of morph-01incmethyl p-tert-octyl phenoxy ethoxy ethyl chloride with 2.5 grams of ethyl chloroacetate at loo-200 C. for four hours. The viscous 011 was extracted with hot water, and the aqueous solution clarified with adsorbent clay and activated silica. The clear, amber, aqueoussoiution contained (p-chloro-ethox ethoxy) -(p-tert-octyl) benzyl carbethoxymethyl morpholiniumchloride: clflnciiiiocimocmcl CI-N-CHaC O 0 Grill C 5 CH3 o A quaternary ammonium salt was prepared by heating 8 grams of morpholinomethyl p-tertoctyl phenoxy ethoxy ethyl chloride with 3.5 grams of nitrobenzyl chloride at 140-185 C. for four hours. .(p-chloroethoxyethoxy)-(p-tert-octyl) -benzyl nitro-benzyl morpholinium chloride was a viscous dark oil, soluble in water with suds.

Example 4 of dicyclohexylamine, 11 grams of water, and 11 grams, of sodium hydroxide. The mixture was stirred seven hours at 79-'95 C.; washed with water, and clarified by agitation with 15 grams of Y active charcoal, The viscous yellow oil was dicyclohexylamino-methyl p-t'ert-octyl phenoxy ethoxy ethyl chloride, having the formula:

A quaternary ammonium salt was prepared by heating 10 grams of dicyclohexylaminomethyl ip-tert-octyl phenoxy ethoxy ethyl chloride with 3 grams of ethyl chloroacetate for five hours at' A mixture of grams of dimethylaminomethyl p-tert-octyl phe'noxy ethoxy ethyl chloride (preparedas in Example 2), grams of 25% dimethylamine, 1000 grams of water, and 20 grams of sodium hydroxide was stirred and heat-' ed in an autoclave for 6.5 hours at 95-159 C. (at 15-90 lbs. gauge pressure). The reaction mixture cooled overnight, and the oil layer was separated. washed with water, and distilled in vacuo. The clear yellow oiL boiIing at I'm-190 C. at 1 mm. pressure. was dimethylaminomethyl p-tertoetyl phenoxy ethoxy'ethyl dimethylamine, in: the iormula: c

hav-

Hs /CH| NCH|ce l(clHiI) O GIHIO CIHCN cm cm A quaternary ammonium salt was prepared y mixing 8 grams of dimethylaminomethyl p-tertoctyl phenoxy ethoxy ethyl dimethylamine with 5.6 grams of methyl iodide. An exothermic reaction took place, and the mixture was cooled. The sohd mass was recrystallized from ethylene 5 dichloride and petroleum ether (90400' 0.).

The dimethylamin'omethyl p-tert-octyl phenoxy ethoxy ethyl dimethylamine di-methiodide was obtained as a colorless crystalline solid, soluble in water, andhaving the formula:

on, 7 0H, cm ucmcimwirrm cimo Cam en'- cm on,

A quaternary ammonium salt was also prepared by mixing 8 grams of dimethylaminomethyl p-tert-octyl phenoxy ethoxy ethyl dimethylamine with 6 grams of diethyl sulfate. An exothermic reaction occurred yielding a viscous paste when cooled,-'which was clearly soluble in water with suds. The di-quaternary salt had the following formula:

' cm. a cm.

' cmkcmcimwimoommocm cm CHI/ CH:

osoiocar,

soioc'sm v Ezample 6 360 grams of 25% dimethylamine solution was addedto 32 grams of di- (chioromethyl) phenoxy ethyl chloride and the mixture stirred and heated 14 hours at ii-69 C. Asolution of 12 grams" of sodium hydroxide in 120 cc. of water was added, and the mixture stirred for five hours, The mixture was filtered, and the filtrate extracted four times with benzene. The benzene was distilled oil! and the residual oil distilled in vacuo.

The yellow oil boiling at 1 10-140 CQ/l mm. was di (dimethylamino methyllphenoxy ethylene, having the formula:

EN (011:): Example 7 omen, o

, A quaternary ammonium derivative was prepared by stirring amixture of 40 grams of di- (morpholinornethyl) phenoxy ethoxy ethyl chloride, 22 grams of benzyl chloride, and 125 grams distilled to remove water -insoluble' impurities. A

smallamount of heavy brown 'oillayer was separated on on standing, and the quaternary amproduct was a mixture -135-165 C. The the viscous sticky oil was separated from the asoaaso.

crcmclmwmiocimcl atC.forthreehours. Themixturebecame veryvlscousandwhenthemixturewascooled, thequaternaryammoniumsaltwasobtainedas a solid which was soluble in water.

Example 8 180 grams of chloromethyl phenoxy ethyl acesome di-chloromethyl phenoxy ethyl acetate), 1080 grams of 25% dimethyl amine, grams of water, and 80 grams of sodium hydroxide were stirred in an autoclave and heated iive hours at mixture cooled overnight, and

aqueous layer withthe aid of benzene. The solvent was .distilled oil. and the residual oil distilled in vacuo. The amino "alcohol,

\ formed 'by substitution of the halogen and am- -monolysis of the ester oups, was obtained as aviscous Oil', b0i]ilig at 133-165} (ill-2 mm. The of dimethyl phenoxy ethanol r N'cmcmocm on 7 I t c V I I and di-(dimethyl) ethanol crhcimocrmorr 1 cm for! cmN \0 Earmple 9 A mixture of 69 gramsof phenyl hydmxyethyl ether, ,CeHsOCzHeOH, 80 grams of paraformaldehyde, and 200 cc. of petrolelnn ether was stirred and saturated with hydrogen chloride for six hours at 30-40 C. The crude oil was washed with water, dried with anhydrous sodium sulfate, illtered, and the solvent distilled oil! under reduced pressure. 7

96 grams of the chloromethyl derivative thus ,obtainedwasaddedtoaeoldmixtureoffiiograms of 25% dimethylamine solution and grams of sodium hydroxide during 20 minutes at 4-20 C.,

andthemixturestirred23homsat20-30'Q.

Theoilwasseparatedtakenupinbenaene,

' washed with water, dried with anhydrous sodimn sulfate, and distilled in vacuo. The dimethylaminomethyl derivative of phenoxy ethanol was obtained as a clear, 'paleyellow oil, boiling at -160 C./2 mm. The product was a mixture of the monoand di-dimethyl derivatives having the formulas:

(cmmwmclmocimon (awes me-11.00.11.011

A quaternar ammonium salt was prepared by heating'four grams oi the dimethylaminomethyl derivative of phenoxy ethanol obtained above and three grams of n- -hexyl at 795 C. The hot viscous reaction mixture was ee-e ,(aontainingllll!- bromide for a half-hour water.

3 Example A mixture or 62 grams oi phenoxy acetone, 81 grams or 37% formaldehyde, and 300 grams or dioxane was stirred and saturated with hydrogen chloride for seven and one-half hours at ill-30 C. The clear dark brown solution was poured into a large volume of ice water, the oil extracted with benzene, washed, and dried.

The benzene solution of di-(chloromethyl) phenoxy acetone, containing also some chloro methylphenoxy acetone, was added to a cold mixture of 180 grams oi! 25% dimethylamine solution and 40 grams of sodium hydroxide at-1020 C., and the heterogeneous brown mixture stirred hours at -30" C. The benzene layer was distilled in .vacuo, and the dimethylamino methyl derivative was obtained as a clear yellow oil boil-- ing at 120-155 C./2 mm., sparingl solublein water, but clearly soluble in dilute hydrochloric acid. The product i was di-(dimethylamino-' methyl) henoxy acetone omnNommmoomooon,

mmcnm containing also some dimethyiarninomethyl phenoxy acetone (omhNommmoomcoom Example 11 containing also some dl-morpholinomethyl-phenoxy acetyl morpholine:

omen, omcn o cmcm-ocmcon o CH|CH| NH, OHiClEh Cs Cfis H. H: o Example 13 3"! grams of chloromethyl phenoxy ethyl laurate, ClCHzCsHsOCzHsOCOCnI-Iza, was added to 8 cold mixture of 37 grams of aniline, 4 grams of sodium hydroxide, and grams of water during ten minutes at 2 to 4 C. The viscous paste was diluted with 50 cc. of water and stirred 25 hours at 420 C. The oil layer was taken up with the aid -01 benzene, washed twice with water, and steam-distilled three hours. The residual oil layer was taken up in benzene, dried, and stripped in vacuo. A brown oil remained which crystallized on standing. This was anilinomethyl phenoxy ethyl laurate:

i CcHaNI-ICHzCcHsOCzHsOCOCnHz:

7 Example 14 A mixture or 180 grams oi phenoxy ethyl acetate, CsHsOCaI-IsOCOCHz, 244 grams c137 tormaldehyde solution, and 200 grams of concentrated hydrochloric acid was stirred and saturated with ethyl ether, CsHsOCzI-LOH, 120 grams of paraformaldehyde, and 300' grams of dioxane was stirred and saturated with hydrogen chloride for 15 hours at 50-60 C. and 4'hours at ill-20 C. The reaction mixture was poured into 1 liter of ice water, the oil layer separated and taken up in 300 cc. of'benzene, dried with anhydrous sodium sulfate and filtered. Half oithe benzene solution was stripped in vacuo to give a clear amber oil which was di-chloromethyl phenoxy ethanol, containing also some'chloromethyl phenoxy ethanol.

245 grams of the benzene solution of the chloromethyl derivative thus obtained was added to a cold mixture of 540 grams 0! 25% dimethylamine solution and 120 grams of sodium hydroxide during 15 minutes at 010 C. and the turbid milky solution stirred 25 hours at 10-20 C. The oil layer was separated, taken up in benzene, washed with water, dried, ,andd istilled in vacuo., A clear, colorless oil was obtained. boiling at 150-170 C./2 mm., which was di-dimethylaminomethyl phenoxy ethanol, containing also some dimethylaminomethyl phenoxy ethanol.

Example 12 vent was distilled oil and the oil distilled in vacuo.

A viscous deep yellow oil was obtained, boiling at 237-275 C./1 mm., which was morpholinomethylphenoxy acetyl morpholine:

CHsCHs CHsOEs Nomomo cmooN OHN I hydrogen chloride for six and one-half hours at Bil-40 C. The oil layer was taken up inbenzene,

washed with ice water, dried with anhydrous so-' dium sulfate, and filtered. 450 grams of a banzene solution of chloromethyl phenoxy ethyl acetate and di-chloromethyl phenoxy ethyl acetate was obtained, and this was divided into two parts for the following experiments.

200 grams of a benzene solution of monoand di-chloromethyl phenoxy ethyl acetate was added to a cold mixture 01 120 grams 0! water, 20 grams 01 sodium hydroxide, and 113 grams or dodecyiamine at 10'-11 C., and the mixture stirred 15 hours at 11-25 C. The oil layer was separated, washed twice with water, and steam-distilled. The residual oil layer was taken up in benzene, washed with water, dried with anhydrous sodium sulfate, and distilled in vacuo. The clear amber oil, boiling at 170-245 C./3 mm. was dodecylaminomethyl phenoxy ethyl acetate:

Ci2H25NHCH2CaH4OC2H4OCOCI-Ia Example 15 200 grams or the benzene solution oi monoand di-chloromethyl phenoxy ethyl acetate prepared in Example 14 was added to a cold mixture of grams of water, 20 grams or sodium hydroxide, and 128 grams 0! Z-ethyl hexylamine, and the mixture stirred 15 hours at 15-25 C. The oil layer was separated, washed with. water, and steam-distilled. The residual oil layer was taken up in benzene, washed, dried, filtered, and distilled. The clear amber oil boiling at 120-260 C./2 mm. was a mixture of 2-ethylhexylamino methyl phenoxy ethyl acetate C4HQCHCH3NHQH|CQH|OC$H4OCOCHI 2H: and di-(2-ethylhexylam'ino methyl) phenoxy ethyl acetate CHICECHsNHCHsCeflaOCtfliOCOOH;

' ,m mNncmcnclm Ezample 16 1 A mixture of 177 grams of p-tert-octyl-ph noxy-ethoxyethoxysethyl dodecyl ether,

CaHnCH4OC2H4OCzHiOCzH4OCuHas 43 grams of 37% formaldehyde solution, and 200 grams concentrated hydrochloric acid was stirred and saturated with hydrogen chloride for 19 hours at 40-60" C. The oil layer was separated,

I taken up. in benzene, washed with ice water, and

850 g. 01' a milky emulsion was obtained which could not be salted out. This contained chloro- -t t cctyl phenoxy-ethoxyethoxy-ethy dodecyl ether, and was divided into two parts to the following experiments. 1

382 grams of the emulsion thus prepared, containing chloromethyl p-tert-octyl phenoxy ethoxy-ethoxy-ethyl dodecyl ether,

emcm cm crmrrcmcano cnno c,n,o 0.11.0 cum,

CHSCH! 1H1! Example 17 382 grams of the emulsion prepared in Example 16, containing chloromethyl p-tert-octyl phenoxyethoxy-ethoxy-ethyl dod'ecyl ether.

was added to a cold mixture of 100 grams of water, 20 grams oi. sodium hydroxide, and 100 grams of monoisopropyl amine, and the mixture stirred 15 hours at 20-25'C. Then 20 cc. of 25% sodium hydroxide solution was added and stirring continued for five hours. The oil layer was separated, taken up in benzene, washed, dried,

and distilled in vacuo. The clear red oil, boiling. at 150-250 C./2 mm. was isopropylamino methylp-tert-octyl phenoxy-ethoxy-ethoxy ethyl lauryl ether CNCHICIHIO CgHsO C1H|0 C:H|O CHE];

C Hz 0H" According to this invention compound of the general formula (halogen-CH2) nArXAY react with primary, secondary, or tertiary amines to form compounds of the formula (ZCI-IzMArXAY wherein Z represents a nitrogenous group such as H H a a a c aseasse In these groups a, b, and c are aliphatic, alicyclic, aralkyl, or aryl groups, e is a saturated divalent group. I is unsaturated trivalent hydrocarbon group, and d ison anion.

when Y is a halogen, there may also be formed compounds-oi the type ZCI-h) sArXAZ wherein Z and 2' may be the same or diiierent amino nitrogen groups as defined above.

We claim: 1. Compounds of the formula (ZCHz) AroAhalogen wherein Z represents a member of the class consistlng of secondary amine groups and tertiary amine groups, n is an integer having a value from one to two, inclusive, Ar is a carbocyclic aromatic group, and A is a member or the class consisting of alkylene groups and alkylene groups the chain of which is interrupted by oxygen to form divalent aliphatic hydrocarbon groups of at least two carbon atoms each.

2. Compounds of the formula (ZCHa) nphenyl0A-halogen wherein Z represents a member of the class consisting of secondary amine groups and tertiary amine groups, n i an integer having a valuefrom one to two, inclusive, and A is a member oi! the class consisting of alkylene groups and alkylene groups the chain-of which is interrupted by oxygen to form divalent aliphatic hydrocarbon 'groupsoi at least two carbon atoms each.

. 3. Compounds 01' the formula (ZCH2)1IA1'OCH2CH2OCH2CH2C1 wherein Z represents amember of the class con- I sisting of secondary amine groups and tertiary amine groups, n is an integer having a value from one to two inclusive, and Ar is a phenyl nucleus.

4. A compound of the formula CHI nomoamcimoocimocimci on. h 5. A compound of the formula lnhoclmocimci CHsCHl wherein n is an integer having a value-from one to two inclusive.

6. A method 01' preparing aminomethyl aryl aliphatic ether halides which comprises reacting between about 20 C. and about C.-in the presence of a strong base a non-tertiary. amine and an ether halide oi the formula 1 I (halogenCHz) sArOAhalogen wherein n represents an integer from one to two inclusive, Ar is a carbocyclic aromatic nucleus, and A is a member of the class consisting of .alkylene groups and alkylene groups the chain of which is interrupted by oxygen to form divalent aliphatic hydrocarbon chains of at least two carbon atoms each.

7. A method 01' preparing aminomethyi phenyl aliphatic ether halides which comprises reacting between about 20 C. andaboutlOO" C. in the presence of a strong base a non-tertiary amine and an ether halide of the formula (halogenCHz) npheny1--OAha1ogen wherein n represents an integer from one to two inclusive and A is a member of the class consisting of alkylene groups and alkylene groups the chain of which is interrupted by oxygen to form divalent aliphatic hydrocarbon chains of at least two carbon atoms each.

8. A method of preparing secondary aminomethyl phenyl aliphatic ether halides which comprises reacting between about 20 C. and about 100 C. in the presence of a strong base a primary amine and a halomethyl ether of the formula (halogenCHz) whenyl-O-A-halogen wherein n is an integer having a value from one to two inclusive and A is a member of the class consisting of alkylen groups and alkylene groups the chain of which is interrupted by oxygen to form divalent aliphatic hydrocarbon chains of atleast two carbon atoms each.

9. A method of preparing tertiary aminomethyl phenyl aliphatic ether halides which comprises reacting between about 20 C. and about 100 C. in the presence of a strong base a. secondary amine and a halomethyl ether of the formula (halogenCHa) nphenyl-0-Ahalogen (halogenCHz) whenyl-OCHzCI-IaOCHzCHzCI wherein n is an integer having a value from one to two inclusive.

11. The method of claim 10 in which the amine is a secondary amine.

12. The method of claim 10 in which the amine is a primary amine.

CLINTON W. MACM'UILEN. HERMAN A. BRUSON. 

